Process for producing oxygenated organic compounds



Patented Aug. 23, 1932 UNITED su s FATE N omcs RALPH L. naown Ann wumu w. onnLL, or rrr'rsnunen, rnnnsnvanm 'rnocnss non rnonucmc oxxennarnn on'a'amc comroum 80 Drawing.

The invention relates generally to a process for treating relatively inexpensive saturated hydrocarbons or paraflins, such as petroleum products containing ethane, propane, butane and higher hydrocarbons for. conversion 0 such products into valuable unsaturated com- I pounds such as olefins, that may be converted into various other'valuable materials, such as alcohols, aldehydes, and the like. Such a process, broadly speaking, isold but it is the object of'the present invention to improve the efliciency of the process, making it possible to utilize the original starting materials to the best advantage. It has been found 5 impossible tocompletely crack parafiines or saturated hydrocarbons in a single cracking treatment and, at the same time, to produce the maximum yield. of olefines from the original starting materials. Accordingly, recir-', culation of theuncracked paraflines through the cracking chamber is resorted to. To do this, however, it is, of course,'necessary to separate the residual paraifins from the other products so that the .paraflins" may be returned to the cracking chamber. Since however, corresponding 0 efins and parafiin s having thesame number of carbons, for example,

pgpylene and propane, have substantially such as fractional distillation, but, according the same boiling point, such separation cannot be readily efiected by ordinary methods to applicants invention, may be best carried outeither by hydration or by combinedh dration and polymerization. ofthe olefins to produce materials of different boiling points from the pa-raflins, such as alcohols, ethers I i and the like, After such hydration and/o1" m paraflins may be separated from the oxidation polymerization of the olefins, the residual products and may. then be recirculated through the cracking chamber.

. In commercial practice when saturated hydrocarbons such as butane, propane or the like are used as raw materials in the production of alcohols and ethers, two distinct processes are generally used; one comprising th'e chlorination of the hydrocarbon followed by the treatment of the chlorinated product with Application-filed September 1927.. Serial'No. 221,129.

an alkali, the reactions being represented by;

Equations 1 and 2 for the production 3 20.114011 -H2O' (distilled i'n pres-.

'caustic alkali asin the above'example, or

hydrolized with steam. These processes are not direct in. that reactions with acids or.

acid radicals and with alkalis are part of the process.

process. v y

Among. the objects of our invention are (1 'To utilize saturated hydrocarbons which are available in large quantities and which are not adaptable for use as motor fuel, in the preparation of ethers, which are adaptable for use as-a blending agent in the mixing of alcohols with gasolines or the like, in the production of motor fuels.

(2) To make .alcohols and ethrs from saturated hydrocarbons'by a continuous process.

(3) To make low priced raw materials for the production of synthetic esters, essential I y oils and the like from low-priced hydrocarbon compounds.

Briefly the process consists in crackingthe saturated. hydrocarbons producing. unsaturated hydrocarbons such as olefins, and subsequently causing theiunsaturated hydrocarbone to react with steam under pressure in the presence of a-catalyst yielding alcohols, 'ethers, mixtures of the two, or other oxygenated products: the latter step being subject matter for our patent application Serial No. 198,202, filedJune 11, 1927.

The difi'erent steps of our process are colacting'as shown iii the following more complete description. 'For the purpose of exemplification a single saturated hydrocarbon referred to here,

namely propane; The

These steps are eliminated in our A C2. 4, and C l-I1 out of the cracking appara- I tus. The second step comprises compressing the products from the cracking apparatus with or without cooling as found necessary, eliminating theH and CH by the liquefaction of the remaining constituents comprising the unsaturates and the homologs of CH The third step comprises introducing the recovered mixture containing the unsaturates, along with steam, under pressure greater than atmospheric and preferably in the vapor phase, into a reaction chamber and causing chemical reaction to take place therein while the reacting substances are under pressure greater than atmospheric and at a temperature above 100 degrees C. by the aid of a catalyst.

The fourth step comprises removing the reaction products which includean alcohol or an ether or both according to conditions as described in'our patent application Serial No. 198,202, from the remaining products which may include C H C H unsaturates and H 0. When higher hydrocarbons than propane (C H are used as raw materials there may be, and normally would be some saturated hydrocarbons higher in the series than propane. The fifth step comprises the introduction of the latter products; namely and chiefly, the saturated hydrocarbons, into the cracking apparatus with the hydrocarbonsused in step 1 for the production of unsaturates. It .will be noted that the products thus recirculated do not include appreciable amounts of hydrogen,ACO CO and N which usually appear in the end products in the commercially employed methanol process.

Our reactions are carried out preferably in the vapor phase and thereforeit is neces} sary to adjust temperatures and pressures to suit the requirements-of the difierent hydrocarbons used and reaction products made.

This relation obviously is based upon the" vapor pressures of the different hydrocarbons, H 0 and reaction products formed. Up to the critical temperature there is a'pressure above which' one can not operate satisfactorily and economically in the vapor phase and that pressure is the pressure at which liquefaction takes place. Above the critical temperature this definite relation does not exist. v I I Catalysts adaptable for use in our process and "the temperature-pressure relations in carrying out the different steps of said proc ess are discussed, alluding again to the above mentioned five steps, as follows:

In Step 1, using propane again as an example, the cracking of the latter for the production ofuns'at'urates maybe carried on at a pressure which is substantially atmospheric pressure; the reaction being substantially represented by Equation 4.

(4) Sufficient (O I-l 0 H, C H +H CH,,+ (3 H, +C l-l with a result favorable to the production of the maximum amount of unsaturates. Aluminum oxide is one catalyst which aids in carrying this class-pf reactions toward comple tion at lower temperatures than otherwise possible.

It is found that at higher cracking temperatures than about 600 to 900 degrees centigrade the tendency for carbon to formas a' result of cracking increases with increments of temperature; this varies in extent with the different catalysts, with the velocity of saturated hydrocarbons through the cracking apparatus and with the nature and pro erties of'the hydrocarbon compounds use as raw. materials. It seems to be a property of hydrocarbon compounds of high molecular weight to break up into molecules oflower molecular weight more readily than their homologs of lower molecular weight.

Upon recirculating the gases from the abovenamed Step 5, that is, upon passing them through the crackin apparatus of Step 1, there would normal y be a tendency for the concentration of H (II-I and C H were it not for the provision for their re- 'moval at the completion ofSte 1. It will be noted that when ethyl alcoho ethyl ether ormixtures are the desired end products, it

is essential to produce in Step 1 the maxi III as large a conversion of C H into CJL as possible in Step" 1. It appears that in the cracking Of C H according to reaction Numbered 5 the time of reaction ordinarily is slow at 67 5 degrees (5) O H,= 0,11 31,270 calories to 800 degrees centigrade without a catalyst. when cracked at temperatures materially higher than the-latter temperature'there are also formed C, CH and other products; at

such temperatures the conditions are not favorable for the maximum 'eld of C l-L,

therefore it becomes essentia to crack the 5 a temperature preferably be .parafiins at as low a temperature as possible in order to produce (3 H and to crack (3 H in the most economicmanner. This we accomplish by the use of catalysts, employing ow 900 degrees Centigrade for cracking (LI-I and about 800 degrees centigrade for cracking propane and butane. Equation 5 shows that v1 volume of C H yields 2 volumes of gas by an endothermic reaction. Obviously any increase in the Concentrationof H or increase in pressure on the system in Step 1, namely in the cracking apparatus, will normally tend to reverse the reaction of Equation 5 and decrease the yield of C IL. Accordingly'we prefer 'to crack the C H at pressure not greatly in excess of atmospheric, realizing that lowpressures during cracking favor the maximum (1 H; yield, and we prefer to have the minimum amount of H in the recirculating gases. Natural gas sometimes contains 15 per cent'or more of C H which latter can readily be converted by the herein described process to C H OH, C H O. C H or mixtures of the two; the H formed-can, with beneficial results, be introduced into the remaining CH gas if desired :the latter mixture not being used in our process.

When the cracking temperatures employed in Step l-aresufliciently high and when the lower monohydric alcohols or simple ethers are the final products sought, the

process is more simple than otherwise, since at temperatures at which H, decomposes the higher members of the homologeous series a so decompose ;,the higher members of the series decomposing normally at lower temperatures than CZH When using as raw materials hydrocarbons of higher molec- 'ular weight than (3 H and C H there are numerous factors to consider and control. For example, it is possible to crack, O I-I with the production of an appreciable amount of amylene .(C H or, at 'higher' temperatures or under different conditions crack it' more completely recovering chiefly? C l-L, C H and C H or still more complete- 1y as already discussed. When'a mixture of hydrocarbons is employed as a base material and cracked under vconditions favorable for the formation of a series of olefins such as C H;, C H C,H 0 1-1 etc.,' the separation of unsaturates from the parafiins which ac,-

company them is not an easy matter without thedestruction of'one or the other series ofhydrocarbons. The boiling points of thelower members-of the-paraflin series are sub- .stantiallythe same as those of the olefin series comparing hydrocarbons having the same Ethylene has "310W critical temperatureand therefore can readily be separated from its number of; carbon atoms in" each 'case."

Propyl-- pletely separated respectively from propane and butane by physical means. Therefore. in producing alcohols and ethers of higher molecular weight by our process-it is some-- times found desirable or economic to allow one or more members of the paraffin series to pass along with the unsaturates into the reaction chamber of Step 5 even though they do not enter into chemical reaction with steam therein. Upon completing the reac- '75 tions of Step 5 and formation of alcohols and ethers it is foundthat the properties of the latter substances are so difierent from those of the parafiins that the latter can readily be separated'from the former and again introduced into the cracking apparatus of Step 1. Since, upon cracking, the 'parafiins of high molecular weight yield besides olefins and H paraflins of lower molecular weight it is desirable, in operating a multiplicityof v units each at different cracking temperatures to conduct the particular paraffins from. Step 5 to the particular cracking apparatus wherein it can be most effectively used. For example, it would hardly be economical in -most cases, to circulate (1 H and C H when it is desirable to produce C H --in the cracking step and (LI-LOH in the reaction chamber. It would be better under these conditions to conduct the C H and (3 H, to cracking apparatus wherein t is desirable to produce C H It will be noted that the paraffins can readily be separated from the alcohols and ethers'and from one another, hence itis possible to use them most effectively in recirculation; in general it is preferable to circulate the paralfins-residual to Step 5, in

. the production of higher alcohols and ethers in the reaction chamber of Step 5, to a cracking apparatus adapted and operated forthe production of olehns suitable for the pro duction of lower alcohols d ethers. This step bringsin the inte rtion of multiple units inthe separate production of a multiplicity of ethers and alcohols. no

Referring again to Step 1,- the cracking process, it is found that whereas (3 H can readily be cracked yielding C H and H at, elevated temperatures, there is a strong tend- This fact explains the 'different and widely varied results reported by different 'investi- M gators of the (1 H, cracking reactions at different' temperatures. Rapid-cooling at the end of Step 1 obviates this to a certain extent. The H is removed in our process before the cracked products enter the reaction chamber or are ag'ain'heated, otherwise there would 'by a union of-H and (1 H, seriously decreasing the efliciency of the process. The removal of H at this point is an important step.

, Alluding now to Step-2, the compressing" and liquefying-phase of the process, we be- 13.6

for a recombination andjformation of lieve we have found commercial application for the phenomena that the members of the olefin series of high molecular weight polymerize more readily than those of lower molecular weight; this phenomena not being- Since in reactions of the latter type a decrease in volume accompanies polymerization increments inpressure tend to hasten the reac- Y tions. We have succeeded-in polymeriz ng isobutylene at 380 degrees C. at atmospheres pressure; and by the aid of catalysts such as A101 PCl, and others, this reaction can be carried out at lower temperatures and lower pressures. The element of time is an important factor in such reactio'nsfhaving vgreater significanceat the lower temperatures and pressures than at higher ones. Ethylene also can be polymerized in a similar manner at slightly higher temperatures.

Upon polymerizing these substances we got end products comprising paraflins, cycloparafiins and unsaturates. 'It will be noted that the products from, Step 1 contain H as well as unsaturated hydrocarbons and We find that it is possible to cause H to combine preferentially with the unsaturates ofhigher molecular weight than 28 by controlling the temperatures and pressures in Step 2. Thus we have in Step 2, two possible and distinct types of reactions under control, namely polymerization and hydrogenation, the former being represented by Equation 6, the latter by Equation 7 When those paraflins are cracked in Step 1 i which yield olefins higher in the series than C H it is a simple matter to separate them from the latter andconvert them to saturated hydrocarbons adaptable for lubricating stock or other use by combining the reactions shown b example in Equations 6 and 7, us-

ing the ydrogen produced as a by-product in the cracking phase,-Step 1., The latter reactions may be carried out in the liquid' ghase using olefins higher in the series than H1 taking advantage of theknown properties of catalysts to speed them. Finely divided or reduced metals are known to cata lyze hydrogenation and salts or compounds,

whether or not polymerization and hydroge- 'natioi1. are induced in this step the olefins or. other unsaturates desired for use in Step 2,

are separated as completely as is economicalparatus'fo'r Step '1.

emma ly possible from the remaining constituents by any suitable means, and are then compressed to the pressure desirable for their use in Step 3, heated when necessary and introduced along with H O, into the reaction'chamber of Step 3. In the latter step the reactions, already alluded to as subjectmatter for a previous patent application, are of a nature represented by Equations 8, 9, 10, 11, 12, and 13.

are separated from gases which may comprise parafiins and some unsaturates and are separated from each other when so desired using known methods for such se aratiom The gases are conducted to the crac 'ng ap- The products leaving the reaction chamber are hot and under considerable pressure and in reducing the temperature and cooling, an engine, multiple stage turbine, other power generating unit or the like may be used thus converting the heat energy into mechanical energy and simultanleously fractionally condensing, and cooling the reaction products. The exhaust, pressure can be so controlled that only products having hoiling points above certain'limits can condense. In other words the fractional condensation in this manner is controlled by knowledge of the vapor pressure(the temperature-pressure relations) or the different alcohols and ethers. Any suitable means of fractional separation may be used. I

Referring to Equation 13, we have found, as shown, that under some conditions there is a tendency fora certain amount of polymerization accompanying the reaction of olefins with steam, particularly in the'presence of a catalyst. Utilizing this reaction it-is possible to makehigher alcohols or ethers from olefins of low molecular weight. This in turn sim lifies the cracking process making. it possible to crack at a temperature which will destroy the higher olefins and yield chiefly olefins of lower molecular weight ,whichdatter can "more readilybe separated 'from theproducts accompanying it resulting from cracking, We have found that certain catalysts, including mixed catalysts, aid in producing such molecular rearrangement and have successfull used salts containing an inor anic acid ra ical such as Alz(SO4) A suita le mixed catalyst for use in the reaction chamber comprises A1 0 and a salt containing an acid radical, for example In carrying out the different steps of our.

process we find that the most economic conditions for the production of the end products and various intermediate products are not always identical with those favoring maximum yield per unit of raw material. For example in cracking hydrocarbons for the production of unsaturates it is sometimes an advantage to conduct the cracking at high temperatures, up to 1000 degrees C. or even higher, the yield of .unsaturates being lower per un t of hydrocarbon used in this instance, but the totalproduction of unsaturates per unit of time may be higherbecause .of conditions relating to'heat transfer rates at the different temperatures and other factors. We therefore do not care to. limit ourselves with respect to temperatures employed in the cracking phase, Step 1, It is believed that cracking processes are old in the art the reactions which pens to be a gas under normal conditions.

The cracking chamber has not been described becauseit is not claimed herein as new and because different types of cracking apparatus which are not new may be used.

A refractory lined chamber having an inlet and an outlet traversable from said inlet to sad outlet by a fluid, having refractory contact-material arranged in the path of, said v fluid, having-means for introducing hydroin carrying out Step 1.

; oxygen-containing that at about' 40 to atmospheres pressure carbon compounds therein and having means for heating said contact material, which latter material may be or may contain catalytic materal. will function as a cracking chamber The products resulting from cracking may be separated into fractions and selected fractions onlv admitted to chemical reaction with steam. or all of theunsaturates thus made mav be used together in, the production of compounds. We find and at a temperature above 205 de ees C.

onl those olefins higher in the )SBPIBS than, {3, 10 will condense upon subsequently cooling and maintaining the pressure. O I-I will condense at approximately 200 degrees;

' the same manner to about 150 degrees C.

C., or lower. Upon subsequently cooling in C,H will condense. At 97 degrees C. C l-I, condenses at about 50 .atmospheres pressure; 0 4 remaining in the, gaseous state at all pressuresuntilthe temperature is reduced to approximately 10 degrees C. .It is thus possible to separate these components and polymerize and hydrogenate individual components as desired, using selected olefins for reaction with steam in the subsequent step.

The hydrogenation and polymerization are conducted inthe vapor phase for the olefins lower in the series than 0 H The temperatures and pressures optimum for the reactions of unsaturates with steam in the formation of oxygen containing compounds vary for the. different compourids formed. These gas reactions, exemplified in Equations 8 to 13, are accompanied by a decrease in volume and it is evident that an increase in pressure favors the reactions; the pressure is limited only because of cost'or mechanical conditions. I at 200 degrees to 400degrees 0. suitable pressures are those which will allow the reacting substances to remain in the gaseous state. Water at 200 degrees 'C. is in the gaseous state at pressures less than about 16' atmospheres whereas at 330 degrees G it is in the gaseous state up to about 130 atmospheres, Consideration is. given to the vapor pressure of the. reacting substances andtheir partial pressures in a given mixture and an economic temperature and an economic pressure are selected as optimum for a given set of conditlons.

When highly superheated steam is used inthe reaction chamber the temperature of the unsaturated hydrocarbons introduced therewith may be lower than otherwise. Thus when making alcohols, when the quantity of Usually in working steam is in large excess of the amount of the olefins used, this method of operating is some-' times advantageous.

' We realizefully that with complete polymerization of unsaturated hydrocarbons the resultingproducts will ordinarily possess the properties of saturated hydrocarbons and therefore will not readily combine with H O forming oxygenated products} however we find that under the influence of mixed cata lvsts and under the conditions which we emplov there is a orodnctioii of a certain amount (if-higher alcohols from simpler unsaturates. We believe the explanation of .the forma: tion of the latter alcohols as describedis found in the simultaneous hydration and polvmerization. These reactions are conceivable as a direct union ofcarbon to carbon temperature above 100 degrees C. to the action co-occuring with the hydration 'ofadjoining carbon atoms of the ethylene-linkages involved, or as resulting through molecular rearrangement simultaneous with hydration reactions. a

We find that iron, preferably on a carrier, polymerizes (H, at 360 degrees centigrade even at atmospheric pressure. Higher pressures favor this class of reactions. At slow velocity and at 425 to 450 degreescentigradedecomposition takes place when ethylene alone is passed over iron catalyst at atmospheric pressure, carbon being deposited.

Using pressures above atmospheric as in our process and carrying out these reactions in the presence of steamthe decomposition effect withthe accompanying deposition of carbonis minimizedu We claim:

A 1. A cyplic' process for treating saturated products formed and conducting the gaseousv non-oxygenated residuals of reaction come hydrocarbons for conversion into valuable prisinglargely saturated hydrocarbons back into a cracking chamber and into cracking reactions; Y v v 2. A cyclic process for treating saturated synthetic products includm' galcohols and ethers with the reed cry and recirculation of residuals of the reaction, ,which comprises first, cracking said hydrocarbon compounds in a suitable cracking chamber by the application of heat,and producing thereby said unsaturated hydrocarbons; second compressing and separating them along with saturated hydrocarbons having similar boiling points from H and CH, produced during said cracking; third subjecting them along withthe separated saturated hydrocarbonsunder pressure greater than atmosphericand at a of H 0 in the presence of a solid catalyst adapted to catalyze hydration reactions but incapable of entering into said reactions;

thereby forming from them the'correspond mg oxygenated compounds; fourth, expanding the reaction products to a lower pressure,

' condensing the oxygenated products formed,

separating them from the gaseous residuals of reaction including largely paraflins, and

I finally conducting said gaseous residualsback into a cracking chamber and cracking reactions.

3. A cyclic process for-treating saturated hydrocarbons for conversion into valuable synthetic products, including alcohols and ethers with the recovery and recirculation of residuals of the reaction, which comprises first, cracking saidhydrocarbon compounds in a suitable cracking chamber by'the application of heat, producing thereby said unsaturated hydrocarbons; second, compressing the resulting roducts and separating therefrom a para and an olefin hydrocarbon having substantially the same boiling points; third, subjecting said separated hydrocar bonsunder pressure greater than atmospheric, at a temperature above IOOdegrees C. to the action of H 0 in the presence of a solid catalyst adapted to catalyze hydration reactions, in a suitable reaction chamber, thereby forming a corresponding oxygenated compound from said olefin; fourth, condensing the said oxygenated product formed, separatingit from the gaseous residuals and finally conductin at least a portion of said gaseous residuals ack intoacracking chamber and cracking reactions.

4. A cyclic process for treating saturated hydrocarbons for conversion into valuable synthetic products, including alcohols and ethers with the recovery and recirculation of residuals of the reactlon, which comprises first, cracking said hydrocarbons in a suitable cracking chamber by the application of heat, producing reaction products containing said unsaturated hydrocarbons; second, separating unsaturated hydrocarbons from said reaction products by preferential condensation; third, subjecting said unsaturated hydro-carbons to the action ofpredetermined amounts of water under pressure greater than atmospheric and at a temperature higher than 100 degrees C. in the presence of a catalyst adapted'to catalyze hydration reactions in a suitable reaction chamber, causing direct chemical reaction to occur between said water and said separated unsaturated hydrocarbons resulting in the formation of the corresponding oxygen-containing compounds and fourth, removing said oxygen-containing compound fromreaction residuals, conducting at least a portion of said residuals back into a cracking chamber and cracking reactions: the relative amounts of alcohols and ethers formed varying with and dependent upon the relative con- Ill centration ofthe reactants in said reaction chamber, a high concentration of said water favoring the formation of a high relative -amount of alcohols and vice versa.

5. A cyclic process for treating saturated j hydrocarbons for conversion into valuable synthetic products, including-alcohols and ethers with the recovery and recirculation of 85 tion of H under pressure greater than atin a suitable cracking chamber by the application 'of heat producing thereby a product containing a plurality of said unsaturated hydrocarbons; second, separating a lurality of selected olefins from said product liquefaction; third, subjecting said selecte olefins expanding and cooling the products of reaction, separating said hydration products from gaseous non-oxygenated residuals by liquefaction and finallyconducting at least a portion'of said residuals back into a cracking v chamber and cracking reactions.

6. A cyclic process for treating saturated hydrocarbons for conversion into valuable synthetic products, including-alcohols and ethers with the recovery and recirculation of grees i and causing preferentialpolymerizaresiduals of the reaction, which comprises first, cracking said hydrocarbon compounds in a cracking chamber in thepresence of a,

catalyst of the type adapted to catalyze cracking reactions with the minimum ormation of carbon, by the application of heat, producing thereby a product containing H and said unsaturated hydrocarbons; second, separating from said product by fractional condensation those selected unsaturated hydrocarbons adapted for making particular oxygen-contalning compounds; third subjecting said selected unsaturated hydrocarbons to the acmospheric, at a temperature above 100 degrees C. in the presence of a solid catalyst adapted to catalyze hydration reactions in a reaction chamber, causing direct chemical reaction to occurbetween them and said H O-forming the corresponding oxygen-containingcompounds, fourth,cooling the products of reaction, separating therefrom said particular oxygen-containing compounds,- and finally conducting at least a portion oi-the residuals of reaction back into a cracking chamber and cracking reactions.

7. A cyclic process for treating saturated hydrocarbons for conversion into valuable synthetic products, including alcohols and ethers with the recovery and recirculation of residuals of the reaction,"whic comprises cracking'said hydrocarbon compounds in a cracking chamber by the application of heat,- producing a product containing H and u saturates including olefins compressing said product, exposing itto a catalyst adapted to catalyze the polymerization and hydrogenation of unsaturated hydrocarbons While under pressure and at altemper'ature above. 100 de tion and hydrogenation of unsaturates having a molecular weighthigher than 56 byliliiitin'g sa1d temperature, said pressure and-the time of contact of said product. with said catalyst i to units unfavorable for the polymerization and hydrogenation of unsaturates having? lower molecular weights; separating olefins from ,the pol merized and hydrogenated roduct and subjecting them to the actionof I 0 under pressure greater than atmospheric at a temperature higher than 100 degrees C. in the presence of a solid catalyst adapted to catalyze hydration reactions in a reaction chamber, causingdirect chemical reactions to occur between them and said H O, forming the corresponding oxygen-containlng comvpounds, expanding and cooling the reaction products, separating therefrom said oxygencontaining compounds and conducting the remainder of said reaction products to a crackolefins.

'8. A cyclic process for treatlng saturated hydrocarbons for conversion into valuable separated olefins to the action of H 0 under pressure greater t n atmospheric at a temperature higher than 100 degrees C. in the presence of a solid catalyst adapted to catayze hydration reactions in a reaction chamber, causing chemical reactionto occur form ing a mixture of ethers and alcohols containing a large or small percentage amount of said alcohols accordingly as the amount ofsaid H O used in said reaction chamber is large or small relative to the, amount of said ing chamber for the further production of I i olefins used; subsequently cooling and fractionally condensing said mfiture of ethers and alcohols, separating them from entrained hydrocarbons and recirculating the latter hydrocarbons through acracking chamber.

9. cyclic process for treating saturated hydrocarbons for conversion into valuable synthetic products, including alcohols and ethers with the recovery andrecirculation of residuals of the reaction, which comprises cracking said hydrocarbon compounds "in a cracking chamber by the application of heat, producing a product containing a plurality of olefins; compressing said product and separating therefrom by liquefaction particular olefins adapted for the production of particu- 'lar mixed ethers;'subjecting said separated particular olefins to the action of H 0 under pressure greater than atmospheric at a temperature above 100 degrees O; in the presence of a catalyst adapted to catalyze? hydration reactions in a reactionphamber, forming said concentration in said reaction chamber being s b tantially 2 molecules of olefins to 1 molesynthetic products, including alcohols and ethers with the recovery and recirculation of residuals of thereaction, which comprises cracking aliphatic hydrocarbons having a greater molecular weight than 28 by the application of heat toproduce a product containing a plurality. of olefins; compressing said product and separating therefrom in known manner amixture of olefins andsatu- .rated hydrocarbons having substantially the same boiling points as said olefins; subjecting said separated olefins to the action of H 0 under pressure greater than atmospheric at a temperature greater than 100 degrees C. in the presence oi? a solid catalyst adapted to catalyze hydration reactions in a reaction chamber, forming the corresponding mixture of alcohols, the concentration of thewreacting substances being substantially in the proportion 2 molecules of said H O to lolefin molecule; subsequently cooling and condensing said mixed alcohols, separating them from entrained hydrocarbons, and finally recirculating the latter hydrocarbons through a cracking chamber.

. 11. A cyclic process for treating saturated hydrocarbons for conversion into valuable synthetic products, including alcohols and ethers with the recovery and recirculation of residuals of the reaction. which comprises cracking a plurality .of said hydrocarbons in a cracking chamber by the application of heat of such intensity that the resulting products contain an appreciable amount of olefin hydrocarbons along with hydrogen; compressing said products and separating said olefin hydrocarbons from said hydrogen by liques faction: subjecting said olefin hydrocarbons separated from said hydrogen, while under pressure greater than one atmosphere and at a temperature above 100 degrees centigrade in the vapor phase, to the action of steam in the presence of a solid catalyst adapted to catalyze hydration reactionsin a reactionchamber, forming oxygen-containing compounds the compositions of which vary aecording to the relative concentrations of said steam and said olefin hydrocarbons in said reaction chamber, being chiefly hydroxides when the said relative concentration of steam,

a cracking chamberjfor the further producsynthetic products, including alcohols and ethers with the recovery and recirculation of residuals of thereaction, which compnses c'racking' said hydrocarbon compounds ina cracking chamber by the application of heat,

' forming unsaturatesof low molecular weight along with hydrogen; cooling the product thus formed to a temperature below the cr1t1- cal temperature of ethylene, compressing it,

liquefying said unsaturates, them from the gaseous remainder 0t sai product, heatin them, subjecting them while heated and un er pressure greater than atmospheric in the vapor phase to the action of steam in thepresen'ce of a solid catalyst adapted to catalyze both polymerization and-hydration reactions, causing some of said unsaturates of low molecular weight to combine 1n part, polymerizing to more complex unsaturates, causing said steam .to react wlth both said partially polymerized and unpolymerized unsaturates forming oxygen-containlng compounds; subsequently expanding, cooling and condensing said oxygen-containing compounds, separating them from entrained hydrocarbons and conducting the latter hydrocarbons. back to a cracking chamber for the subsequent production of additional unsaturates.

13. In the process described in claim 12,-

the step comprising the simultaneous polymerization and hydration of unsaturated hydroc'arbons under pressure greater than atmo'spheric, at a temperature higher than 190 degree C. in a reaction chamber, by the aid of a mixed catalyst comprising alumlnum oxide and at least one salt containing an morganic' acid radical.

14. In the process described in claim 12, the-step comprising the simultaneous polymerization and hydration! of unsaturated hydrocarbon compounds of low molecular weight by the aid of a catalyst while under temperature higher than 100'degrees C. in a reaction chamber forming oxygen containing compounds of relatively high molecular weight; said catalyst containing both alumiacid radical.

15. A cyclic process for treating saturated hydrocarbons for conversion ,into valuable synthetic products, including alcohols and others with the recovery andrecirculatiop of residuals of 'the reaction, which comprises cracking. said hydrocarbon compounds in-a cracking chamber by the application of heat,

forming products comprising hydrogen paraifins and unsaturates, separating some of separating num oxide and a salt containing an inorganic pressure greater than atmospheric and at a said parafis and-the olefins separately from the remaining products by compression and liquefaction, recirculating said separated paraflins through said cracking chamber,

compressing them to a pressure greater than atmospheric, heating said separted olefins to a temperature higher than 5100 degrees (3.,

introducing them while thus heated and tun der pressure along with steam into a reaction chamber, causing chemical reaction to occur between them and said steam by virtue of a solid catalyst adapted to catal ze hydration reactions in said reaction chamber, and finallycooling and condensing the reaction products. Y

16. A cyclic rocess for tre'ating saturated hydrocarbons ibr conversion into valuable synthetic products, including alcohols and T ethers with the recovery and recirculation of residuals of the reaction, which comprises cracking said-hydrocarbon compounds in a 0 cracking chamber by the application of heat at a temperature sufiiciently high for sub-' stantially complete cracking of parafiins and olefins of high molecular weight, cooling the resulting products, compressing them and se arating therefrom ethylene, heating said et ylene and introducing it, while under pressure greater than one atmosphere, and at a temperature higher than 100 de ees G. p 1 along with steam into a reaction 0 amber, 3o causmg said ethylene and said steam to react chemically, by virtueof a solid catalyst adapted to catalyzehydration reactions forming reaction products comprising 0 gen-'- containing compounds, separating sai .oxy-

v gen-contaming compounds fromsresiduals of reaction and recirculating said residuals through a cracking chamber. I

RALPH BROWN. 7 WILL ODELL. 

